JPS599892B2 - How to obtain a radiograph - Google Patents
How to obtain a radiographInfo
- Publication number
- JPS599892B2 JPS599892B2 JP50040577A JP4057775A JPS599892B2 JP S599892 B2 JPS599892 B2 JP S599892B2 JP 50040577 A JP50040577 A JP 50040577A JP 4057775 A JP4057775 A JP 4057775A JP S599892 B2 JPS599892 B2 JP S599892B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- photographic
- silver halide
- dye
- dyes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 silver halide Chemical class 0.000 claims description 97
- 229910052709 silver Inorganic materials 0.000 claims description 58
- 239000004332 silver Substances 0.000 claims description 58
- 239000000839 emulsion Substances 0.000 claims description 52
- 230000001235 sensitizing effect Effects 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 89
- 230000035945 sensitivity Effects 0.000 description 26
- 206010070834 Sensitisation Diseases 0.000 description 14
- 230000008313 sensitization Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 11
- 230000003595 spectral effect Effects 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052771 Terbium Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 8
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 206010073306 Exposure to radiation Diseases 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- AGJZCWVTGOVGBS-UHFFFAOYSA-N 1,1'-diethyl-2,2'-cyanine Chemical compound C1=CC2=CC=CC=C2N(CC)\C1=C\C1=CC=C(C=CC=C2)C2=[N+]1CC AGJZCWVTGOVGBS-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- UPPYOQWUJKAFSG-UHFFFAOYSA-N 1,3-benzoxazol-5-ol Chemical compound OC1=CC=C2OC=NC2=C1 UPPYOQWUJKAFSG-UHFFFAOYSA-N 0.000 description 1
- SAHAKBXWZLDNAA-UHFFFAOYSA-N 1,3-benzoxazol-6-ol Chemical compound OC1=CC=C2N=COC2=C1 SAHAKBXWZLDNAA-UHFFFAOYSA-N 0.000 description 1
- WJBOXEGAWJHKIM-UHFFFAOYSA-N 1,3-benzoxazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2OC=NC2=C1 WJBOXEGAWJHKIM-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YCOYDSQEOWWYDT-UHFFFAOYSA-N 3,3-dichloroprop-2-enal Chemical compound ClC(Cl)=CC=O YCOYDSQEOWWYDT-UHFFFAOYSA-N 0.000 description 1
- YRXNYGPDPLYTQX-UHFFFAOYSA-N 3,5-dichloro-1-hydroxy-2,4-dihydrotriazine Chemical compound ON1NN(Cl)CC(Cl)=C1 YRXNYGPDPLYTQX-UHFFFAOYSA-N 0.000 description 1
- NDUHYERSZLRFNL-UHFFFAOYSA-N 4,6-dimethyl-1,3-benzoxazole Chemical compound CC1=CC(C)=C2N=COC2=C1 NDUHYERSZLRFNL-UHFFFAOYSA-N 0.000 description 1
- RWNMLYACWNIEIG-UHFFFAOYSA-N 5,6-dimethyl-1,3-benzoxazole Chemical compound C1=C(C)C(C)=CC2=C1OC=N2 RWNMLYACWNIEIG-UHFFFAOYSA-N 0.000 description 1
- IYKOEMQMBVZOSI-UHFFFAOYSA-N 5-(trifluoromethyl)-1,3-benzoxazole Chemical compound FC(F)(F)C1=CC=C2OC=NC2=C1 IYKOEMQMBVZOSI-UHFFFAOYSA-N 0.000 description 1
- PGOGTWDYLFKOHI-UHFFFAOYSA-N 5-bromo-1,3-benzoxazole Chemical compound BrC1=CC=C2OC=NC2=C1 PGOGTWDYLFKOHI-UHFFFAOYSA-N 0.000 description 1
- VWMQXAYLHOSRKA-UHFFFAOYSA-N 5-chloro-1,3-benzoxazole Chemical compound ClC1=CC=C2OC=NC2=C1 VWMQXAYLHOSRKA-UHFFFAOYSA-N 0.000 description 1
- MHWNEQOZIDVGJS-UHFFFAOYSA-N 5-ethoxy-1,3-benzoxazole Chemical compound CCOC1=CC=C2OC=NC2=C1 MHWNEQOZIDVGJS-UHFFFAOYSA-N 0.000 description 1
- ZRMPAEOUOPNNPZ-UHFFFAOYSA-N 5-fluoro-1,3-benzoxazole Chemical compound FC1=CC=C2OC=NC2=C1 ZRMPAEOUOPNNPZ-UHFFFAOYSA-N 0.000 description 1
- IQQKXTVYGHYXFX-UHFFFAOYSA-N 5-methoxy-1,3-benzoxazole Chemical compound COC1=CC=C2OC=NC2=C1 IQQKXTVYGHYXFX-UHFFFAOYSA-N 0.000 description 1
- UBIAVBGIRDRQLD-UHFFFAOYSA-N 5-methyl-1,3-benzoxazole Chemical compound CC1=CC=C2OC=NC2=C1 UBIAVBGIRDRQLD-UHFFFAOYSA-N 0.000 description 1
- NIFNXGHHDAXUGO-UHFFFAOYSA-N 5-phenyl-1,3-benzoxazole Chemical compound C=1C=C2OC=NC2=CC=1C1=CC=CC=C1 NIFNXGHHDAXUGO-UHFFFAOYSA-N 0.000 description 1
- JJOOKXUUVWIARB-UHFFFAOYSA-N 6-chloro-1,3-benzoxazole Chemical compound ClC1=CC=C2N=COC2=C1 JJOOKXUUVWIARB-UHFFFAOYSA-N 0.000 description 1
- FKYKJYSYSGEDCG-UHFFFAOYSA-N 6-methoxy-1,3-benzoxazole Chemical compound COC1=CC=C2N=COC2=C1 FKYKJYSYSGEDCG-UHFFFAOYSA-N 0.000 description 1
- SZWNDAUMBWLYOQ-UHFFFAOYSA-N 6-methylbenzoxazole Chemical compound CC1=CC=C2N=COC2=C1 SZWNDAUMBWLYOQ-UHFFFAOYSA-N 0.000 description 1
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- JKVRUCRFECOCME-UHFFFAOYSA-N O(Br)Br.[Gd] Chemical class O(Br)Br.[Gd] JKVRUCRFECOCME-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- UPIZSELIQBYSMU-UHFFFAOYSA-N lanthanum;sulfur monoxide Chemical class [La].S=O UPIZSELIQBYSMU-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000002601 radiography Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
- C09K11/7771—Oxysulfides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/167—X-ray
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
Description
【発明の詳細な説明】
本発明は・・ロゲン化銀写真感光材料を用いて放射線写
真を得る方法およびそのための写真感光材料の改良に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of obtaining a radiograph using a silver halide photographic material and to improvements in the photographic material for this purpose.
本発明はさらに詳しくは、ハロゲン化銀写真感光材料を
放射線螢光増感スクリーンと接触させてイオン化放射線
に露出した後写真処理することによつて放射線写真像を
得る方法およびそれに用いられるハロゲン化銀写真感光
材料に関するものである。X線記録材料には、通常ハロ
ゲン化銀写真フイルムと共に、X線に対する記録感度を
高めるために増感紙(Intensifyingscr
een)やケイ光板を用いることが多い。More particularly, the present invention relates to a method for obtaining a radiographic image by exposing a silver halide photographic material to ionizing radiation by contacting it with a radiation fluorescent intensifying screen and then subjecting it to photographic processing, and the silver halide used therein. It relates to photographic materials. X-ray recording materials usually include silver halide photographic film and intensifying screens to increase the recording sensitivity to X-rays.
een) or a fluorescent plate are often used.
過剰なX線々量の被暴が人体に有害な作用をもつので、
できるだけ少いX線線量でX線写真を得るため、X線に
対する記録感度を高める工夫が行われている。例えば、
ハロゲン化銀写真乳剤を高感度化することは勿論、X線
ケイ光増倍管(X−Rayimageintensif
ier)を用いるシステム、固体X線像増巾器(SOl
ld一Statelightamplifier)を用
いるシステムなど開発されている。しかしながら、何れ
の場合も最終的には、ケイ光像としてゼラチン・ハロゲ
ン化銀感光材料に記録されることになる。従来、この目
的に用いられた螢光体はストロンチユウムによつて活性
化された硫酸バリウム、鉛によつて活性化された硫酸バ
リウム、銀によつて活性化された硫酸バリウム、鉛で活
性化されたタングステン酸カルシウム〔CaWO,〕、
銀によつ ;て活性化された硫化亜鉛、ユーロビウムに
よつて活性化されたリン酸バリウム〔Ba,(PO4)
,〕のような青色の螢光体である。Exposure to excessive amounts of X-rays has harmful effects on the human body,
In order to obtain X-ray photographs with as little X-ray dose as possible, efforts are being made to increase recording sensitivity to X-rays. for example,
In addition to increasing the sensitivity of silver halide photographic emulsions, X-ray image intensifiers (X-ray image intensifiers)
system using a solid-state X-ray image intensifier (SOl
A system using the ld-Statelightamplifier has been developed. However, in either case, the image is ultimately recorded on the gelatin/silver halide photosensitive material as a fluorescent image. Traditionally, phosphors used for this purpose have been strontium-activated barium sulfate, lead-activated barium sulfate, silver-activated barium sulfate, and lead-activated barium sulfate. Calcium tungstate [CaWO,]
Zinc sulfide activated by silver, barium phosphate [Ba, (PO4) activated by eurobium]
, ] is a blue phosphor.
とくに医療目的には、放射線写真用・・ロゲン化銀材料
と共に用いられる螢光増感スクリーンは従来ほとんど螢
光体と jして上記タングステン酸カルシウムまたは鉛
によつて活性化された硫酸バリウムを含むものであつた
。最近、医療用のX線撮影の機会が増加していることか
ら高い発光エネルギー強度をもつ螢光増感スクリーンの
研究がなされている。とくに他の 4稀土類元素によつ
て活性化された稀土類オキシサルフアイドおよびオキシ
ハライド螢光体が高い発光エネルギー強度をもつことが
ロツキード・エアクラフト社(LOckheedAir
craftCOrp.)の研究報告などで知られている
。他方、用いられるX線感光材料一直接X線写真材料お
よび間接X線写真材料−は現像、定着処理を含めて取扱
いやすいことが望ましい。Particularly for medical purposes, radiographic...fluorescent intensifying screens used with silver halide materials have conventionally mostly contained barium sulfate activated by the calcium tungstate or lead as the phosphor. It was hot. Recently, as opportunities for medical X-ray imaging have increased, research has been carried out on fluorescent intensifying screens with high luminous energy intensity. In particular, the rare earth oxysulfide and oxyhalide phosphors activated by the other four rare earth elements have a high luminous energy intensity, which has been demonstrated by Lockheed Aircraft Co., Ltd.
craftCOrp. ) is known for his research reports. On the other hand, it is desirable that the X-ray photosensitive materials used, i.e., direct X-ray photographic materials and indirect X-ray photographic materials, be easy to handle, including development and fixing processes.
特に出来るだけ明るい室で取扱われることが望ましい。
この種のX線写真材料は、たとえば富士写真フイルム社
製./167フイルタ一を用いた安全光のもとで取扱わ
れている。富士写真フイルム一滉7フイルタ一の分光透
過率曲線は第1図に示されている。In particular, it is desirable to handle the product in a room that is as bright as possible.
This type of X-ray photographic material is manufactured by Fuji Photo Film Co., Ltd., for example. Handled under safe light using a /167 filter. The spectral transmittance curve of Fuji Photo Film's 7-filter filter is shown in FIG.
すなわち放射線写真用ハロゲン化銀感光材料は、上記の
改良された螢光体から放射線励起によつて放出される緑
色の螢光に対して高感度であつて、他方安全光照明に対
しては低感度であることが望ましい。最近・・ロゲン化
銀写真乳剤を用いる感光材料の現像・定着処理工程は益
々短縮され、60秒〜120秒になつた。In other words, silver halide photosensitive materials for radiography are highly sensitive to the green fluorescence emitted from the above-mentioned improved phosphor upon radiation excitation, but have low sensitivity to safe light illumination. Sensitivity is desirable. Recently, the development and fixing steps for photosensitive materials using silver halide photographic emulsions have been increasingly shortened to 60 seconds to 120 seconds.
このような写真処理では、写真乳剤中に含有された増感
色素は感光材料から流出されにくく、したがつて処理ず
みの写真は、残つた色素によつて汚染(残色と言う)さ
れやすい。緑色波長域の分光増感には、メロシアニン色
素、ヘミシアニン色素、三核シアニン色素もしばしば用
いられている。しかしこれらの色素による分光増感は何
れも分光感度分布が広すぎて、狭い特定な波長域に増感
する目的には不適である。また高感度が得られにくい。
特に高感沃臭化銀写真乳剤の分光増感には、増感率が低
くて不利である。またこれら増感色素に対する強色増感
剤が見出されにくい。この種の目的のためにはJ一凝集
体型シアニン色素の適用が有利であり、又多く知られて
いる。例えばイミダゾロカルボンアニン色素を用いる技
術:米国特許2701198号、2945763号、2
973264号、
3173791号、3364031号、
3397060号、3506443号、特公昭43−4
936号やまたドイツ特許出願(0LS)194475
1号、2011879号、2018687号、2030
326号や、イミダオキサカルボシアニン色素を用いる
技術:特公昭44−14030号などがある。In such photographic processing, the sensitizing dye contained in the photographic emulsion is difficult to be washed out of the light-sensitive material, and therefore the processed photograph is likely to be contaminated (referred to as residual color) by the remaining dye. Merocyanine dyes, hemicyanine dyes, and trinuclear cyanine dyes are also often used for spectral sensitization in the green wavelength range. However, the spectral sensitization using these dyes has too wide a spectral sensitivity distribution and is therefore unsuitable for the purpose of sensitizing to a narrow specific wavelength range. Also, it is difficult to obtain high sensitivity.
In particular, it is disadvantageous for the spectral sensitization of highly sensitive silver iodobromide photographic emulsions because of its low sensitization rate. Furthermore, supersensitizers for these sensitizing dyes are difficult to find. For this type of purpose, the application of J monoaggregated cyanine dyes is advantageous and many are known. For example, techniques using imidazolocarbonanine dyes: US Pat. Nos. 2701198, 2945763, 2
No. 973264, No. 3173791, No. 3364031, No. 3397060, No. 3506443, Special Publication No. 43-4
No. 936 Yamata German Patent Application (0LS) 194475
No. 1, No. 2011879, No. 2018687, 2030
No. 326, and a technique using imidaoxacarbocyanine dye: Japanese Patent Publication No. 14030/1984.
またプソイドシアニン色素を用いる技術:ドイツ特許出
願(0LS)1936262号、仏国特許148805
7号なども知られている。これらの知られたシアニン色
素には高い分光感度を与えるものがあるが、それらは増
感波長が長すぎて、発光感度の高い緑色螢光体の発光ス
ペクトルとよく一致せず、また写真処理後の感光材料上
の残色が多くて、満足すべきものがなかつた。Also, technology using pseudocyanine dyes: German patent application (0LS) No. 1936262, French patent No. 148805
No. 7 is also known. Some of these known cyanine dyes provide high spectral sensitivity, but their sensitizing wavelengths are too long and do not match well with the emission spectra of green phosphors, which have high luminescence sensitivity. There was a lot of residual color on the light-sensitive material, and I was not satisfied with it.
本発明の目的は放射線螢光増感スクリーンと写真感光材
料の組合せにより、高い感度ですなわちより少い放射線
量で放射線写真を得る方法の達成にある。本発明の他の
目的は、放射線螢光増感スクリーンと写真感光材料を組
合せて放射線写真を得る方法において、残色が少く且つ
画像最大濃度の高い放射線写真を得ることにある。The object of the present invention is to achieve a method for obtaining radiographs with high sensitivity, ie, with a lower radiation dose, by a combination of a radiation intensifying screen and a photographic material. Another object of the present invention is to obtain radiographs with little residual color and high maximum image density in a method of obtaining radiographs by combining a radiation fluorescent intensifying screen and a photographic light-sensitive material.
本発明の目的はさらに、最大発光がスペクトルの緑色域
にある放射線螢光増感スクリーンの発光に対する感度が
高く、安全光下で高い安全性をも・つて取扱いができ、
かつ写真処理後の残色が少ない・・ロゲン化銀写真感光
材料を提供することである。A further object of the present invention is to provide a radiation phosphor intensifying screen with a maximum emission in the green region of the spectrum, which has high sensitivity to emission and can be handled with high safety under safe light;
It is an object of the present invention to provide a silver halide photographic material that has little residual color after photographic processing.
本発明のさらに他の目的は迅速現像工程に適する緑色光
感度の高いハロゲン化銀写真感光材料を得るにある。Still another object of the present invention is to obtain a silver halide photographic material with high sensitivity to green light, which is suitable for a rapid development process.
本発明者らは、下記に示す特定増感色素群による組合せ
が、本発明の上記諸目的を効果的に達成することを見出
した。The present inventors have discovered that the combination of specific sensitizing dyes shown below effectively achieves the above objects of the present invention.
即ち、本発明は下記の一般式(I)によつて表わされる
少くとも一つの増感色素と一般式()によつて表わされ
る少くとも一つの増感色素とを組合せて、ハロゲン化銀
写真乳剤に含有せしめることによつて達成された。一般
式(I)式中R。That is, the present invention combines at least one sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the general formula () to produce a silver halide photograph. This was achieved by incorporating it into an emulsion. In general formula (I), R.
はアルキル基(置換アルキル基を包含するものとする)
をあられし、たとえばメチル基、エチル基、n−プロピ
ル基、ヒドロキシエチル基、アセトキシメチル基、エト
キシエチル基などをあられす。R1及びR2は各々アル
キル基(置換アルキル基を包含するものとする)をあら
れす。たとえば無置換アルキル基(たとえばメチル基、
エチル基、ブチル基など)、ヒドロキシアルキル基(た
とえば2−ヒドロキシエチル基、4−ヒドロキシブチル
基など)、アセトキシアルキル基(例えば2−アセトキ
シエチル基、3−アセトキシプロピル基など)、カルボ
キシラジカルをもつアルキル基(例えば2−カルボキシ
エチル基、3−カルボキシプロピル基、2 −( 2
−カルボキシエトキシ)エチル基、など)、スルホラジ
カルをもつアルキル基(例えば2−スルホエチル基、3
−スルホプロピル基、3−スルホブチル基、4−スルホ
ブチル基、2−ヒドロキシ−3−スルホプロピル基、2
−( 3 −スルホプロポキシ)エチル基、2−アセ
トキシ−3−スルホプロピル基、3−メトキシ− 2
−( 3 −スルホプロポキシ)プロピル基、2〔2
−( 3 −スルホプロポキシ)エトキシ〕エチル基、
2−ヒドロキシ−3−(3’−スルホプロポキシ)プロ
ピル基など)、アラルキル基(例えばベンジル基、フエ
ニルエチル基など)を表わす。ただし、R1 とR2の
うち少くとも1つはスルホラジカルをもつアルキル基で
あるものとする。Xはシアニン色素において通常用いら
れるアニオン(例えば、塩素イオン、臭素イオン、沃素
イオン、チオシアン酸イオン、p−トルエンスルホン酸
イオン、エチル硫酸イオンなど)を表わす。mはlを表
わす。一般式()
式中、zはベンズオキサゾール核例えばベンズオキサゾ
ール、5−クロルベンズオキアゾール、5−メチルベン
ズオキサゾール、5−ブロムベンズオキサゾール、5−
フルオロベンズオキサゾール、5−フエニルベンズオキ
サゾール、5−メトキシベンズオキサゾール、5−トリ
フルオロメチルベンズオキサゾール、5−ヒドロキシベ
ンズオキサゾール、5−カルボキシベンズオキサゾール
、6−メチルベンズオキサゾール、6−クロルベンズオ
キサゾール、6−メトキシベンズオキサゾール、6−ヒ
ドロキシベンズオキサゾール、5・6−ジメチルベンズ
オキサゾール、.4・6−ジメチルベンズオキサゾール
、5−エトキシベンズオキサゾールなどを表わす。is an alkyl group (including substituted alkyl groups)
For example, methyl group, ethyl group, n-propyl group, hydroxyethyl group, acetoxymethyl group, ethoxyethyl group, etc. R1 and R2 each represent an alkyl group (including substituted alkyl groups). For example, an unsubstituted alkyl group (such as a methyl group,
ethyl group, butyl group, etc.), hydroxyalkyl group (e.g., 2-hydroxyethyl group, 4-hydroxybutyl group, etc.), acetoxyalkyl group (e.g., 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), and carboxy radical. Alkyl groups (e.g. 2-carboxyethyl group, 3-carboxypropyl group, 2-(2
-carboxyethoxy)ethyl group, etc.), alkyl groups with sulfo radicals (e.g. 2-sulfoethyl group, 3-sulfoethyl group, etc.),
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-(3-sulfopropoxy)ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2
-(3-sulfopropoxy)propyl group, 2[2
-(3-sulfopropoxy)ethoxy]ethyl group,
2-hydroxy-3-(3'-sulfopropoxy)propyl group, etc.), aralkyl group (eg, benzyl group, phenylethyl group, etc.). However, at least one of R1 and R2 is an alkyl group having a sulfo radical. X represents an anion commonly used in cyanine dyes (eg, chloride ion, bromide ion, iodide ion, thiocyanate ion, p-toluenesulfonate ion, ethyl sulfate ion, etc.). m represents l. General formula () where z is a benzoxazole nucleus such as benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-
Fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6 -methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, . Represents 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, etc.
R,はアルキル基または置換アルキル基でR1、R2と
同意義、Qは2−チオイミダゾリジン−2・4−ジオン
核例えば2一チオイミダゾリジン一2・4−ジオン核、
3一エチル一2−チオイミダゾリジン−2・4−ジオン
核、3−(4−スルホブチル)−2−チオイミダゾリジ
ン−2・4−ジオン核、3−(2−カルボキシエチル)
−2−チオイミダゾリジン−2・4−ジオン核、3−フ
エニル一2−チオイミダゾリジン−2・4−ジオン核、
3−α−ナフチル−2一チオイミダゾリジン一2・4−
ジオン核、1・3−ジエチル−2−チオイミダゾリジン
−2・4−ジオン核、1−エチル−3−フエニル一2−
チオイミダゾリジン−2・4−ジオン核、1・3−ジフ
エニル一2−チオイミダゾリジン−2・4−ジオン核、
1−(2−カルボキシエチル)−3一フエニル一2−チ
オイミダゾリジン−2・4−ジオン核、1−フエニル一
3−エチル−2−チオイミダゾリジン−2・4−ジオン
核、1−(2−ヒドロキシエチル)−3−フエニル一2
−チオイミダゾリジン−2・4−ジオン核、1−(3−
ヒドロキシプロピル)−3−フエニル一2−チオイミ
5ダゾリジン一2・4−ジオン核、1−(2−カルボキ
シエチル)−3−(p−クロルフエニル)−2−チオイ
ミダゾリジン−2・4−ジオン核、1ーエチル−3−n
−ブチル−2−チオイミダゾリジン−2・4−ジオン核
などを表わす。本発明で用いる緑色発光螢光スクリーン
に用いられる螢光体は好ましくは原子番号39または5
7〜71の元素例えばイツトリウム、ガドリニウム、ラ
ンタン、セリウム等の物質を含むものでフある。R is an alkyl group or a substituted alkyl group having the same meaning as R1 and R2, Q is a 2-thioimidazolidine-2,4-dione nucleus, for example, a 2-thioimidazolidine-2,4-dione nucleus,
3-ethyl-2-thioimidazolidine-2,4-dione nucleus, 3-(4-sulfobutyl)-2-thioimidazolidine-2,4-dione nucleus, 3-(2-carboxyethyl)
-2-thioimidazolidine-2,4-dione nucleus, 3-phenyl-2-thioimidazolidine-2,4-dione nucleus,
3-α-naphthyl-2-thioimidazolidine-2,4-
Dione nucleus, 1,3-diethyl-2-thioimidazolidine-2,4-dione nucleus, 1-ethyl-3-phenyl-2-
Thioimidazolidine-2,4-dione nucleus, 1,3-diphenyl-2-thioimidazolidine-2,4-dione nucleus,
1-(2-carboxyethyl)-3-phenyl-2-thioimidazolidine-2,4-dione nucleus, 1-phenyl-3-ethyl-2-thioimidazolidine-2,4-dione nucleus, 1-( 2-hydroxyethyl)-3-phenyl-2
-thioimidazolidine-2,4-dione nucleus, 1-(3-
(hydroxypropyl)-3-phenyl-2-thioimi
5 Dazolidine-2,4-dione nucleus, 1-(2-carboxyethyl)-3-(p-chlorophenyl)-2-thioimidazolidine-2,4-dione nucleus, 1-ethyl-3-n
-Butyl-2-thioimidazolidine-2,4-dione nucleus, etc. The phosphor used in the green-emitting fluorescent screen used in the present invention preferably has an atomic number of 39 or 5.
7 to 71 elements, such as yttrium, gadolinium, lanthanum, and cerium.
特に有用なものは他の稀土類で活性化された稀土類オキ
シサルフアイドおよびオキシハライド螢光物質例えばテ
ルビウムまたはジスプロシウムで活性化されたランタン
あるいはガドリニウムのオキシブロマイドおよびオキシ
クロライド、テルビウム、ユーロピウムまたはユーロピ
ウムとサマリウムの混合物で活性化されたランタンある
いはガドリニウムのオキシサルフアイドである。かよう
な稀土類螢光物質はドイツ特許1282819号、フラ
ンス特許1540341号、1580544号、202
1397号、フランス特許1473531号に対する追
加特許94579号、米国特許3546128号、34
18246号、3418247号、3705858号、
3725704号、3778615号および1969年
10月29日〜31日サン・フランシスコでのIEEE
ニユクレア・サイエンス・シンポジウムでのケ一・工ー
・ウツカーシヤイムなどによる「稀土類オキシサルフア
イドX一線螢燐光体」なる報告およびアール・エ一・ブ
キャナン;IEEE・トランズアクシヨンズ・オン・ニ
ユクレア・サイエンス1972年2月号、第81〜83
頁に記載されている。Particularly useful are other rare earth activated rare earth oxysulfide and oxyhalide fluorophores such as lanthanum or gadolinium oxybromides and oxychlorides activated with terbium or dysprosium, terbium, europium or europium. It is an oxysulfide of lanthanum or gadolinium activated with a mixture of samarium. Such rare earth fluorescent materials are disclosed in German patent No. 1282819, French patent No. 1540341, 1580544, 202
No. 1397, additional patent No. 94579 to French Patent No. 1473531, U.S. Patent No. 3546128, 34
18246, 3418247, 3705858, 3725704, 3778615 and IEEE in San Francisco, October 29-31, 1969.
A report titled "Rare Earth Oxysulfide February issue, No. 81-83
It is written on the page.
このような新規の稀土類螢光物質、特に他の稀土類例え
ばエルビウム、テルビウム及び/又はジスプロシウムで
活性化されたガドリニウムおよびランタンオキシサルフ
アイドおよびオキシハライドは高度のX線阻止能または
平均吸収力と大なる発光強度をもち、放射線取扱者が実
質的に低いX線量を用いることを可能にする。感光材料
の単位面積当りのハロゲン化銀量が低いことは経済的に
有利であるだけでなく、一般に処理時間とくに定着時間
の短縮に有利である。Such new rare earth fluorophores, especially gadolinium and lanthanum oxysulfides and oxyhalides activated with other rare earths such as erbium, terbium and/or dysprosium, have a high degree of X-ray stopping or average absorption power. It has a large emission intensity, allowing radiation workers to use substantially lower X-ray doses. A low amount of silver halide per unit area of a light-sensitive material is not only economically advantageous, but also generally advantageous in shortening processing time, particularly fixing time.
しかしながら単位面積当りハロゲン化銀量の少い写真感
光材料を用いると、得られる像の最大濃度およびコント
ラストが低下する。微粒子乳剤を用いれば高い最大濃度
をうることはできるが、写真感度が低いから、大量の放
射線露出が必要となる。したがつて、単位面積当りハロ
ゲン化銀量が少なくても充分の最大濃度とコントラスト
が得られしかも感度の高い写真乳剤層が望まれる。本発
明によるとこのような要求が満たされ、感光材料一平方
デシメートル当りの銀量が約8611Ifより小さくて
も好ましい結果を得ることができる。本発明の特徴は一
般式(1)で表わされる5位「フエニル」置換ベンズオ
キサゾール核からなるベンズイミダゾロオキサカルボシ
アニン色素と一般式()で表わされる2−チオイミダゾ
リジンー2・4−ジオン核からなるジメチンメロシアニ
ン色素との組合せを用いて低銀量のハロゲン化銀写真乳
剤を分光増感することにより、低銀量乳剤の最大濃度を
低下させることがなく、螢光増感スクリーンによる発光
に対して高い感度がえられることである。However, when a photographic light-sensitive material containing a small amount of silver halide per unit area is used, the maximum density and contrast of the obtained image are reduced. Although high maximum densities can be obtained using fine grain emulsions, their photographic sensitivity is low and large amounts of radiation exposure are required. Therefore, a photographic emulsion layer is desired which can provide sufficient maximum density and contrast even with a small amount of silver halide per unit area and has high sensitivity. According to the present invention, these requirements are met, and favorable results can be obtained even when the amount of silver per square decimeter of light-sensitive material is less than about 8611If. The features of the present invention are a benzimidazolooxacarbocyanine dye consisting of a benzoxazole nucleus substituted with 5-position "phenyl" represented by the general formula (1) and a 2-thioimidazolidine-2,4-dione represented by the general formula (). By spectrally sensitizing low-silver silver halide photographic emulsions using a combination with a dimethine merocyanine dye consisting of a core, the maximum density of the low-silver emulsion is not reduced, and the dye can be easily sensitized by a fluorescent intensifying screen. High sensitivity to light emission can be obtained.
一般式(1)で表わされる増感色素のうち、R1とR2
が共にスルホラジカルをもつアルキル基の場合に特に高
い感度がえられる。5位メトキシ置換ベンズオキサゾー
ル核からなるベンズイミダゾロオキサカルボシアニン色
素と下記の化学構造式で表わされるメロシアニン色素と
の組合せは米国防衛公開(U.S.Defensive
PubllcatlOn)T9O4O26にて知られて
いる。Among the sensitizing dyes represented by general formula (1), R1 and R2
Particularly high sensitivity can be obtained when both are alkyl groups having sulfo radicals. The combination of a benzimidazolooxacarbocyanine dye consisting of a benzoxazole nucleus substituted with methoxy at the 5-position and a merocyanine dye represented by the chemical structural formula below is disclosed in the U.S. Defensive Publication.
PublcatlOn) T9O4O26.
比較用メロシアニン色素(1)(UST9O4O26の
色素Fに相当)
比較用メロシアニン色素(2)
(UST9O4O26の色素Eに相当)
本発明で用いられる一般式()で表わされZ)5位「フ
エニル」置換ベンズオキサゾール核を有するベンズイミ
ダゾロオキサカルボシアニンと一般式()で表わされる
2−チオイミダゾリジン−2・4−ジオン核を有するジ
メチンメロシアニン色素との組合せは後に実施例(第1
表)で示すごとく、UST9O4O26に記載の組合せ
により高感度である。Merocyanine dye for comparison (1) (corresponds to dye F of UST9O4O26) Merocyanine dye for comparison (2) (corresponds to dye E of UST9O4O26) Represented by the general formula () used in the present invention, Z) 5th position "phenyl" The combination of a benzimidazolooxacarbocyanine having a substituted benzoxazole nucleus and a dimethine merocyanine dye having a 2-thioimidazolidine-2,4-dione nucleus represented by the general formula () will be described later in Example (1st
As shown in Table 1), the combination described in UST9O4O26 provides high sensitivity.
本発明の方法において螢光増感スクリーンにテルビウム
で賦活されたガドリニウムオキシサルフアイド、テルビ
ウムで賦活されたイツトリウムオキシサルフアイド、お
よびテルビウムで賦活されたランタンオキシサルフアイ
ドのいずれか一つ又は二つ以上の混合物を螢光体として
用いたとき、特に高い放射線感度がえられる。In the method of the present invention, one or two of terbium-activated gadolinium oxysulfide, terbium-activated yttrium oxysulfide, and terbium-activated lanthanum oxysulfide are used in the fluorescent intensifying screen. Particularly high radiation sensitivity can be obtained when the above mixture is used as a phosphor.
本発明のもう1つの特徴は本発明の増感色素の組合せを
用いることにより、処理済みの写真要素に増感色素に基
因する残色が小さいことである。Another feature of the invention is that by using the sensitizing dye combinations of the invention, processed photographic elements have less residual color due to the sensitizing dyes.
本発明に用いられる一般式()で表わされる色素のうち
R1とR2の両方がスルホラジカルをもつアルキル基で
ある色素と、一般式()で表わされる色素のうちR3が
スルホラジカルをもつアルキル基をもつ色素との組合せ
は、非常に小さい残色を与える。本発明のもう1つの特
徴は、本発明の増感色素の組合せを用いることにより、
通常X線写真材料などに用いられる完全光フイルタ一(
たとえば富士フイルム製FL7フイルタ一)を用いたセ
ーフライト光に対する充分な安全性がえられることであ
る。Among the dyes represented by the general formula () used in the present invention, both R1 and R2 are an alkyl group having a sulfo radical, and among dyes represented by the general formula (), R3 is an alkyl group having a sulfo radical. The combination with dyes with gives very little residual color. Another feature of the invention is that by using the combination of sensitizing dyes of the invention,
A complete optical filter (usually used for X-ray photographic materials)
For example, sufficient safety against safelight light using Fuji Film's FL7 filter can be obtained.
前記UST9O4O26で知られている色素の組合せで
はセーフライト安全性が悪いことは後の実施例(第2表
)に示すごとくである。本発明のもう一つの特徴は、医
療用放射線写真において一般に用いられるような、0.
7μをこえる平均粒径をもつ粒子の大きいハロゲン化銀
乳剤においても充分高い分光増感がえられることである
。The combination of dyes known from UST9O4O26 has poor safelight safety, as shown in Examples (Table 2) below. Another feature of the invention is that the 0.000.
Sufficiently high spectral sensitization can be obtained even in a large-grain silver halide emulsion with an average grain size exceeding 7 μm.
粒子径の比較的小さい・・ロゲン化銀乳剤に対しては優
秀な分光増感を示す色素でも、しばしば粒子径が大きい
乳剤に対しては分光増感作用の劣るものがある(たとえ
ばメソアルキル置換チアカルボシアニン)。本発明にお
いて用いられる一般式(1)の色素と一般式()の色素
との組合せは、平均粒径0.7μをこえるハロゲン化銀
乳剤、特に平均粒径1.2μをこえるような高感度ハロ
ゲン化銀乳剤に対してすぐれた緑色域分光増感を与える
。本発明に用いられる一般式(1)で表わされるベンズ
イミダゾロ・オキサカルボシアニン色素の〉*典型的な
例を次に挙げる。Even dyes that exhibit excellent spectral sensitization for silver halide emulsions with relatively small grain sizes often exhibit poor spectral sensitization for emulsions with large grain sizes (for example, mesoalkyl-substituted thia carbocyanin). The combination of the dye of general formula (1) and the dye of general formula () used in the present invention is suitable for use in silver halide emulsions with an average grain size of over 0.7μ, particularly in high-sensitivity emulsions with an average grain size of over 1.2μ. Provides excellent green spectral sensitization to silver halide emulsions. Typical examples of the benzimidazolo-oxacarbocyanine dye represented by the general formula (1) used in the present invention are listed below.
ただし本発明に用いる増感色素はこれに限定されない。
本発明に用いられる一般式()で表わされる2−チオ−
2・4−イミダゾリジンジオン核含有ジメチンメロシア
ニン色素の典型的な例を次に挙イ☆げるが、これにより
本発明に使用する増感色素が限定されるものではない。However, the sensitizing dye used in the present invention is not limited to this.
2-thio- represented by the general formula () used in the present invention
Typical examples of dimethine merocyanine dyes containing a 2,4-imidazolidinedione nucleus are listed below, but the sensitizing dyes used in the present invention are not limited thereto.
一般式(1)で表わされる色素は、特公昭44一140
30号、特開昭47−33626号などに記載の増感色
素で、上記明細書を参照すれば当業者は容易に合成でき
、また記載のないものも類似の方法により合成できる。The dye represented by the general formula (1) is
Those skilled in the art can easily synthesize the sensitizing dyes described in No. 30, JP-A No. 47-33626, etc. by referring to the above specifications, and those not described can be synthesized by similar methods.
一般式()で表わされる色素は、米国特許251900
1号同3822136号、英国特許1315773号、
特開昭48−33817号またはF,M.ヘーマ一(H
amer)著の″TheCvanineDyesand
RelatedCOmpOunds″Intersci
eneePubllshers,.NewYOxlc(
1964)511ページ以降を参照すれば、当業者は容
易に合成でき、また具体的記載のないものも類似の方法
により合成できる。The dye represented by the general formula () is disclosed in U.S. Patent No. 251900.
No. 1 No. 3822136, British Patent No. 1315773,
JP-A No. 48-33817 or F.M. Hemaichi (H
``The Cvanine Dyesand'' by Amer)
RelatedCompOunds”Intersci
eneePubllshers,. NewYOxlc(
1964) from page 511 onwards, those skilled in the art can easily synthesize the compounds, and those not specifically described can also be synthesized by similar methods.
本発明においては、個々の増感色素について種種の濃度
で用いうるが、ハロゲン化銀モル当り増感色素の約1.
0×10−5〜約1.0X10−3モルを用いるのが有
利である。Although various concentrations of individual sensitizing dyes can be used in the present invention, about 1.0% of sensitizing dye per mole of silver halide.
Advantageously, from 0.times.10@-5 to about 1.0.times.10@-3 moles are used.
とくにハロゲン化銀モル当り約4×10−5〜1.6X
10−4モルの増感色素を用いるのが有利である。色素
の組合せ使用における使用比率(一般式(1)で表わさ
れる色素/一般式()で表わされる色素のモル比)は約
10/1〜約1/10が好ましく\とくに約5/1〜約
1/5が最も有効である。In particular, about 4 x 10-5 to 1.6 x per mole of silver halide
Advantageously, 10@-4 moles of sensitizing dye are used. The usage ratio in the combination of dyes (molar ratio of dye represented by general formula (1)/dye represented by general formula ()) is preferably about 10/1 to about 1/10, especially about 5/1 to about 1/5 is the most effective.
増感色素の最適濃度は、当業者に公知の方法に従つて、
同一乳剤を分割し、各部分に異なる濃度の増感色素を含
有せしめてその感度を測定する方法により決定すること
ができる。The optimal concentration of sensitizing dye is determined according to methods known to those skilled in the art.
The sensitivity can be determined by dividing the same emulsion, allowing each part to contain a different concentration of sensitizing dye, and measuring the sensitivity.
増感色素の乳剤への添加方法はこの種の分野で良く知ら
れた方法による。The sensitizing dye is added to the emulsion by methods well known in this field.
これらの増感色素は直接に乳剤に分散することもでき、
あるいは最初にピリジン、メチルアルコール、エチルア
ルコール、メチルセロソルブ、アセトンなど(または以
上のごとき溶媒の混合物)の水混和性溶媒に溶解し、あ
る場合には水にて希釈し、またある場合には水のみで溶
解し、これらの溶液の形で乳剤へ添加することができる
。These sensitizing dyes can also be directly dispersed in emulsions,
or first dissolved in a water-miscible solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of such solvents) and diluted with water; These can be added to the emulsion in the form of a solution.
またこの溶解に超音波振動を用いることもできる。その
他、例えば特公昭45−8231号、特公昭44−23
389号、特公昭44−27555号、特公昭44−2
2948号、ドイツ特許出願(0LS) 194793
5号、米国特許3485634号、米国特許33426
05号や米国特許2912343号などに記載されてい
る方法も用いられる。Moreover, ultrasonic vibration can also be used for this melting. Others, such as Special Publication No. 45-8231, Special Publication No. 44-23
No. 389, Special Publication No. 1977-27555, Special Publication No. 1977-2
No. 2948, German patent application (0LS) 194793
No. 5, U.S. Patent No. 3,485,634, U.S. Patent No. 33,426
Methods described in No. 05, US Pat. No. 2,912,343, etc. can also be used.
必要に応じて増感色素は適当な各々溶媒に別々に溶解し
乳剤へ刃1j々に添加することができるし、あるいは各
色素は同一または異なつた溶媒に溶解し、ハロゲン化銀
乳剤へ添加するに先立つてこれら溶液を混合する方法を
とることもできる。If desired, the sensitizing dyes can be dissolved separately in appropriate solvents and added to the emulsion separately, or each dye can be dissolved in the same or different solvents and added to the silver halide emulsion. It is also possible to use a method of mixing these solutions prior to.
増感色素を含有せしめた乳剤を適当な支持体、例えばガ
フス、セルロース誘導体のフイルム、ポリビニル樹脂の
フイルム(例えばポリリスチレンフイルム、ポリ塩化ビ
ニルフイルムなど)、ポリエステルフィルム、合成紙、
バライタ紙、ポリオレフイン被C膜で覆われた写真用紙
などに塗布を行う前に、色素を乳剤全体にわたり均一に
分散させる必要がある。これら増感色素を乳剤に添加す
る時期は乳剤製造工程中、いかなる時期でもよいが、第
2熟成終了後に添加する方が便利である。本発明に用い
られるハロゲン化銀は、例えば塩化銀、臭化銀、沃化銀
、塩臭化銀、沃臭化銀、塩沃臭化銀などのうちいずれで
もよいが沃臭化銀または沃塩臭化銀が有利であり沃化銀
含有率が3モル%をこえない沃臭化銀は特に好ましい。The emulsion containing the sensitizing dye is applied to a suitable support such as gaff, cellulose derivative film, polyvinyl resin film (e.g. polystyrene film, polyvinyl chloride film, etc.), polyester film, synthetic paper,
Prior to coating on baryta paper, polyolefin-coated photographic paper, etc., the dye must be uniformly dispersed throughout the emulsion. These sensitizing dyes may be added to the emulsion at any time during the emulsion manufacturing process, but it is more convenient to add them after the second ripening is completed. The silver halide used in the present invention may be any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc.; Silver chlorobromide is preferred, and silver iodobromide with a silver iodide content not exceeding 3 mol % is particularly preferred.
これら5のハロゲン化銀粒子は公知の方法例えばシング
ノいジニット法、ダブル・ジニット法あるいはエンドロ
ール・ダブル・ジニット法で形成される。更にハロゲン
化銀粒子の結晶構造は内部迄一様なものであつても、ま
た内部(COre)と、それ)と異質の殻(Shell
)とからなる層状構造をしたものや、英国特許6358
41号や米国特許3622318号に記されているよう
ないわゆるコンバージヨン型のものであつてもよい。ま
た潜像を主として表面に形成する型のもの、潜像を粒子
内部に形成する内部潜像型のもの何れでもよい。これら
の写真乳剤は6ザ セオリ一 オブ フオトグラフイツ
ク プロセス(TheTheOryOfPhOtOgr
aphicPrOces8、1ミース(Mees)著マ
グ ミラン(MacMillan)社刊、゛フオトグラ
フイツク ケミストリ一(PhOtOgraphicC
hemistry)″グラフキデ(Grafukide
s)著、フアウンテイン プレス(FOunkginP
ress)社刊等の成書にも記載され、当業者に周知の
アンモニア法、中性法、酸性法等種々の方法で調製し得
る。このようなハロゲン化銀粒子をその形成後、副生し
た水溶性塩類(たとえば硝酸銀と臭化カリウムを用いて
臭化銀をつくつたときは硝酸カリウム)を、その系から
除去するため水洗し、ついで熱処理を化学増感剤の存在
下で行い、粒子を粗大化しないで感度を上昇させること
ができる。また、副生した水溶性塩類を除去しないで、
そのまま用いられることもある。これらの慣用法は上掲
書に記載されている。用いられるハロゲン化銀粒子の平
均直径(例えばプロジエクテツドエリア法、数平均によ
る測定)は約0,7〜2.0μが好ましく、特に1.0
μ〜2.0μの場合に本発明の効果が大きい。These five silver halide grains are formed by a known method such as a single dinit method, a double dinit method, or an endroll double dinit method. Furthermore, even if the crystal structure of silver halide grains is uniform up to the inside, there is also a difference between the inside (COre) and the heterogeneous shell (Shell).
) with a layered structure, and British patent 6358
It may be of a so-called conversion type as described in No. 41 and US Pat. No. 3,622,318. Further, either a type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are based on 6 The Theory of Photographic Processes.
aphicPrOces8, 1 Written by Mees, published by MacMillan, PhOtOgraphicC
hemistry)" Grafukide
s), Founkgin Press
It can be prepared by various methods such as an ammonia method, a neutral method, an acid method, etc. which are well known to those skilled in the art. After forming such silver halide grains, they are washed with water to remove by-product water-soluble salts (for example, potassium nitrate when silver bromide is made using silver nitrate and potassium bromide) from the system, and then Heat treatment can be performed in the presence of a chemical sensitizer to increase sensitivity without coarsening the particles. Also, without removing by-product water-soluble salts,
Sometimes it is used as is. These usages are described in the above book. The average diameter of the silver halide grains used (measured by, for example, the projected area method or number average) is preferably about 0.7 to 2.0 μm, particularly about 1.0 μm.
The effect of the present invention is large in the case of μ to 2.0 μ.
用いられるハロゲン化銀写真乳剤には、通常用いられて
いる化学増感法、例えば金増感(米国特許254008
5号、2597876号、2597915号、2399
083号など);第族金属イオンによる増感、硫黄増感
(米国特許1574944号、同2278947号、同
2440206号、同2410689号、同31894
58号、同3415649号など);環元増感(米国特
許2518698号、同2419974号、同2983
610号など);またはその複合された各種増感法が適
用できる。The silver halide photographic emulsion used can be processed by commonly used chemical sensitization methods, such as gold sensitization (US Pat. No. 254,008).
No. 5, No. 2597876, No. 2597915, 2399
No. 083, etc.); sensitization with group metal ions, sulfur sensitization (US Pat. No. 1,574,944, US Pat. No. 2,278,947, US Pat. No. 2,440,206, US Pat. No. 2,410,689, US Pat. No. 3,1894)
No. 58, US Pat. No. 3,415,649, etc.); cyclic sensitization (US Pat. No. 2,518,698, US Pat.
No. 610, etc.); or various sensitization methods combined therewith can be applied.
更に具体的な化学増感剤としては、チオ硫酸ナトリウム
、アリルチオカルバミド(AllylthiOcarb
amide)、チオ尿素、シスチンなどの硫黄増感剤,
塩化金酸カリ、チオ硫酸金(4)、塩化パラジウム酸カ
リなどの貴金属増感剤:塩化第一スズ、フエニルヒドラ
ジンやレダクトンなどの環元増感剤などを含んでよい。
ポリオキシエチレン誘導体(英国特許
981470号、特公昭31−6475号、米国特許2
716062号など)、ポリオキシプロピレン誘導体、
4級アンモニウム基をもつ誘導体などの増感剤も含んで
よい。More specific chemical sensitizers include sodium thiosulfate and allylthiOcarbamide.
amide), thiourea, cystine and other sulfur sensitizers,
Noble metal sensitizers such as potassium chloroaurate, gold(4) thiosulfate, and potassium chloropalladate; ring element sensitizers such as stannous chloride, phenylhydrazine, and reductone; and the like may be included.
Polyoxyethylene derivatives (British Patent No. 981470, Japanese Patent Publication No. 31-6475, U.S. Patent No. 2)
No. 716062), polyoxypropylene derivatives,
Sensitizers such as derivatives with quaternary ammonium groups may also be included.
感光材料のハロゲン化銀乳剤層には、適当なカブリ防止
剤や安定剤を含有しうる。The silver halide emulsion layer of the light-sensitive material may contain a suitable antifoggant or stabilizer.
また、米国特許2131038号や2694716号な
どに記載のチアゾリウム塩;米国特許2886437号
や2444605号などに記載のアザインデン類(Az
aindenes);米国特許3287135号などに
記載のウラゾール類;米国特許3236652号などに
記載のスルホカテコール類;英国特許623448号な
どに記載のオキシム類、米国特許2403927号、3
266897号、3397987号などに記載のメルカ
プトテトラゾール類、ニトロン;ニトロインタゾール類
;米国特許2839405号などに記載の多価金属塩;
米国特許3220839号などに記載のチオウロニウム
塩;米国特許2566263号、2597915号など
に記載のパラジウム、白金および金等の貴金属塩なども
用いられる。In addition, thiazolium salts described in US Pat. No. 2,131,038 and US Pat. No. 2,694,716; azaindenes (Az
aindenes); urazoles as described in US Pat. No. 3,287,135; sulfocatechols as described in US Pat. No. 3,236,652; oximes as described in British Patent No. 623,448; US Pat.
Mercaptotetrazoles and nitrones described in No. 266897, No. 3397987, etc.; nitrointazoles; polyvalent metal salts described in U.S. Pat. No. 2,839,405, etc.;
Thiouronium salts described in US Pat. No. 3,220,839 and the like; salts of noble metals such as palladium, platinum and gold as described in US Pat. Nos. 2,566,263 and 2,597,915 can also be used.
更に、本発明に用いられるハロゲン化銀写真乳フ剤層に
は現像主薬(例えばハイドロキノン類、カテコール類、
アンノブエノール類、3−ピラゾリドン類、アスコルビ
ン酸やその誘導体、リダクトン類やフエニレンジアミン
類等)を一種または二種以上組合せて含有させることが
できる。Furthermore, the silver halide photographic emulsion layer used in the present invention contains developing agents (such as hydroquinones, catechols,
Annobuenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc.) can be contained singly or in combination of two or more.
現像主薬は・・ロゲン化銀乳剤中及び/または写真要素
中の他の適当な層に含有させてもよい。現像主薬は適当
な溶媒に溶かして、または米国特許2592368号や
仏国特許1505778号に記載されているような分散
物の形で添加されてもよい。The developing agent may be contained in the silver halogenide emulsion and/or in other suitable layers in the photographic element. The developing agent may be added dissolved in a suitable solvent or in the form of a dispersion as described in US Pat. No. 2,592,368 and French Patent No. 1,505,778.
感光材料のハロゲン化銀乳剤層は、種々の有機または無
機の硬膜剤(例えばホルムアルデヒド、クロムアラム、
1−ヒドロキシ−3・5−ジクロロトリアジンソーダ、
グリオキザール、ジクロロアクロレインなど)によつて
硬膜されてもよい。The silver halide emulsion layer of the light-sensitive material is coated with various organic or inorganic hardeners (for example, formaldehyde, chromium alum,
1-hydroxy-3,5-dichlorotriazine soda,
glyoxal, dichloroacrolein, etc.).
感光材料のハロゲン化銀写真乳剤層には塗布助剤例えば
サポニン、米国特許2600831号などに記載のアル
キルアリールスルホン酸塩、米国特許3133816号
などに記載の両性(AmphOteric)化合物など
も含有しうる。The silver halide photographic emulsion layer of the light-sensitive material may also contain coating aids such as saponin, alkylaryl sulfonates as described in US Pat. No. 2,600,831, and amphoteric compounds as described in US Pat. No. 3,133,816.
感光材料のハロゲン化銀写真乳剤は帯電防止剤、可塑剤
、螢光増白剤、現像促進剤、空気カブリ防止剤、色調剤
、カラー・カプラーなども含有しうる。また、目的に応
じて含有されるイラジエーシヨン防止用染料としては例
えば、特公昭41一20389号、特公昭43−350
4号、特公昭43−13168号、米国特許26970
37号、同3423207号、同2865752号、英
米特許1030392号、同1100546号などに記
載されているものが使用される。本発明では通常のゼラ
チン・・ロゲン化銀乳剤が使用されるが、ゼラチンの代
りにたとえばアルブミン、寒天、アラビアゴム、アルギ
ン酸など、またはポリビニールアルコール、ポリビニル
ピロリドンのごとき親水性樹脂またはセルロール誘導体
のような感光性ハロゲン化銀に対し有害な作用をおよぼ
すことのない物質も使用されてよい。The silver halide photographic emulsion of the light-sensitive material may also contain antistatic agents, plasticizers, fluorescent brighteners, development accelerators, air fog inhibitors, toning agents, color couplers, and the like. In addition, examples of anti-irradiation dyes that may be contained depending on the purpose include Japanese Patent Publication No. 41-20389, Japanese Patent Publication No. 43-350
No. 4, Special Publication No. 43-13168, U.S. Patent No. 26970
No. 37, No. 3423207, No. 2865752, British and American Patent No. 1030392, No. 1100546, etc. are used. In the present invention, a conventional gelatin-silver halide emulsion is used, but instead of gelatin, for example, albumin, agar, gum arabic, alginic acid, etc., or hydrophilic resins such as polyvinyl alcohol, polyvinylpyrrolidone, or cellulose derivatives are used. Substances that do not have a deleterious effect on the photosensitive silver halide may also be used.
本発明による色素の組合せに、更に他の増感色素を組合
せて用いることができる。特に一般式(1)で表わされ
る色素及び/または一般式()で表わされる色素と、強
色増感作用のある他の色素としてメチン色素(例えばモ
ノメチンシアニン色素、カルボシアニン色素やアポメロ
シアニン色素)が有利に用いられる。本発明の方法にお
いて、ハロゲン化銀感光材料は放射線露出後現像される
。The combination of dyes according to the invention may be used in combination with other sensitizing dyes. In particular, the dye represented by the general formula (1) and/or the dye represented by the general formula (), and other dyes with supersensitizing action include methine dyes (such as monomethine cyanine dyes, carbocyanine dyes and apomerocyanine dyes). ) are advantageously used. In the method of the present invention, the silver halide photosensitive material is developed after exposure to radiation.
医療用X線写真の目的には早く結果を得るために、迅速
処理されることが好ましい。迅速処理するための現像液
は高い現像活性を必要とし、それは高活性現像薬または
それと超加成性作用のある現像薬との組合せを用い、現
像液を適当なPHまで(たとえばPH9〜12)アルカ
リ性をもたせることにより得られる。現像液にはまた通
常の添加剤例えば亜硫酸塩、ヒドロキシルアミンまたは
その誘導体、硬膜剤、カブリ防止剤(例えばベンゾトリ
アゾール、5−ニトロベンズイミダゾール、5−ニトロ
インタゾール)、ハロゲン塩(例えば臭化カリウム)、
ハロゲン化銀溶剤、色調剤、その他ジメチルホルムアミ
ド、ジメチルアセタミド、N−メチルピロリドンなどを
含んでよい。特開昭48−55730号で知られるよう
な発色処理工程により放射線単色色素像をうることもで
きる。For medical X-ray photography purposes, rapid processing is preferred in order to obtain results quickly. A developer for rapid processing requires high development activity, which means that a highly active developer or a combination thereof with a superadditive developer is used to adjust the developer to an appropriate pH (for example, pH 9-12). Obtained by making it alkaline. The developer solution also contains customary additives such as sulfites, hydroxylamine or its derivatives, hardeners, antifoggants (e.g. benzotriazole, 5-nitrobenzimidazole, 5-nitrointazole), halogen salts (e.g. bromide). potassium),
It may contain a silver halide solvent, a toning agent, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. A radiation monochromatic dye image can also be obtained by a color development process as known from JP-A No. 48-55730.
一方、特公昭40−23310号で知ら☆色素(3)色
素(4)
また、比較用に用いた色素(5)は、下記の構造を☆れ
るような反転カラー処理のように、初めにメトール、ハ
イドロキノンのような白黒現像を行い次いで色素像を形
成する処理を行つてもよい。On the other hand, dye (3) dye (4) known from Japanese Patent Publication No. 40-23310 (4) and dye (5) used for comparison was first methol , hydroquinone, etc., followed by processing to form a dye image.
また上記処理工程中銀像を漂白せずに色素像+銀像の形
で用いることもできる。次に本発明を実施例を挙げて説
明するが、本発明は勿論これに限定されるものではない
。It is also possible to use the silver image in the form of a dye image plus a silver image without bleaching the silver image during the above processing steps. Next, the present invention will be described with reference to Examples, but the present invention is of course not limited to these.
実施例 1
平均粒子サイズ1.3μの沃臭化銀からなる写真j乳剤
(AgIl.2モル%;ゼラチン(め/AgNO3(F
f)0.4;0.75モル銀塩/Kg乳剤)をつくつた
。Example 1 A photographic emulsion consisting of silver iodobromide with an average grain size of 1.3 μm (AgIl. 2 mol %; gelatin (me/AgNO3 (F
f) 0.4; 0.75 mol silver salt/Kg emulsion) was prepared.
安定剤として乳剤Kg当り500ηの5−メチルーJメ
[ヒドロキシ一S−トリアゾロ〔1・5−a〕ピリミジ
ンを添加した。このハロゲン化銀乳剤に第1表に示すよ
うに増感色素を添加した。比較用に用いた色素(3)及
び色素(4)は、下記の構造をもつイミダゾロオキサカ
ルボシアニン色素で、前記Def.Pub(T9O4O
26)中に記載の色素A及びBに夫々相当する。500 η/kg of emulsion as a stabilizer.
[Hydroxy-S-triazolo[1.5-a]pyrimidine was added. Sensitizing dyes were added to this silver halide emulsion as shown in Table 1. Dye (3) and Dye (4) used for comparison are imidazolooxacarbocyanine dyes having the following structures, and the Def. Pub(T9O4O
26) Corresponds to dyes A and B described in 26), respectively.
もつメロシアニン色素である。It is a merocyanine pigment.
色素(5)
上記乳剤を、青色に染色された(Bluetinted
)ポリエチレンテレフタレート支持体の下塗りされた両
面に、各面上に一平方メートル当り銀3.87に相当す
るハロゲン化銀を含むハロゲン化銀乳剤層がえられるよ
うに、塗布した。Dye (5) The above emulsion was dyed blue (Bluetinted).
) A polyethylene terephthalate support was coated on both primed sides in such a way that a silver halide emulsion layer containing silver halide equivalent to 3.87 silver per square meter was obtained on each side.
各乳剤層の上に一平方メートル当り17の塗布量でゼラ
チン保護層を設けた。塗布物に次なようにしてX線照射
した。第2図に示した如き発光スペクトルを有するテル
ビウムで活性化されたガドリニウムオキシサルフアイド
(Gd2O2S)螢光紙2枚の間に塗布物をはさみ、光
学ウエツヂをフイルムと螢光紙の間に挿入してX線照射
した(線量25ミリレントゲン)。露出後の写真要素を
下記に示す工程に従いローラー搬送型処理機を用いて現
像処理した。A protective layer of gelatin was applied over each emulsion layer at a coverage of 17 per square meter. The coated material was irradiated with X-rays in the following manner. The coating was sandwiched between two sheets of terbium-activated gadolinium oxysulfide (Gd2O2S) fluorescent paper having an emission spectrum as shown in Figure 2, and an optical wedge was inserted between the film and the fluorescent paper. X-ray irradiation was performed (dose 25 milliroentgen). The exposed photographic element was processed using a roller conveyor processor according to the steps described below.
現像液および定着液の組成は次の通りである。The compositions of the developer and fixer are as follows.
現像液!0
第1表には用いた増感色素の組合せについて得られた相
対感度(カプリ濃度プラス0.5の濃度における露光量
の逆数の相対値)と、カブリ濃度(支持体濃度を含まず
)を示した。Developer! 0 Table 1 shows the relative sensitivity (relative value of the reciprocal of the exposure amount at a density of Capri density plus 0.5) obtained for the combinations of sensitizing dyes used and the fog density (excluding support density). Indicated.
第1表から、本発明の色素の組合せが増感螢光スクリー
ン下の発光には高感度を与え、とくにUST9O4O2
6中の色素の組合せよりも高感度であることが明らかで
ある。From Table 1, it can be seen that the combination of dyes of the present invention provides high sensitivity for emission under an intensifying fluorescent screen, especially for UST9O4O2
It is clear that the sensitivity is higher than that of the combination of dyes in 6.
また、腐7の比較例(増感色素(1−5)と比較用色素
−5の併用)は、本願の増感色素(1一5)と(−4)
の併用に比べると、感度は、およそ59%しか得られな
い。In addition, the comparative example of Fu7 (combination of sensitizing dye (1-5) and comparative dye-5) is the combination of sensitizing dye (1-5) and (-4) of the present application.
Compared to the combined use of , the sensitivity is only about 59%.
またカブリも多いことがわかる。/168の比較例(比
較用色素−4と(−4)の併用)は本願の増感色素(1
−5)と(−4)の併用に比べると、およそ62%の感
度しか得られない。実施例 2
平均粒子サイズが1.5μの沃臭化銀粒子からなる写真
乳剤(AgIl.4モル%、ゼラチン(y)/AgNO
3(f)0.5、0.8モル銀/I<9乳剤)をつくつ
た。It can also be seen that there is a lot of fog. /168 comparative example (combination of comparative dyes -4 and (-4)) is the sensitizing dye of the present application (1
Compared to the combination of -5) and (-4), only about 62% sensitivity can be obtained. Example 2 Photographic emulsion consisting of silver iodobromide grains with an average grain size of 1.5μ (AgIl.4 mol%, gelatin (y)/AgNO
3(f) 0.5, 0.8 mol silver/I<9 emulsion) was prepared.
安定剤として乳剤Kg当り500Tf9の5−メチルJ
メ[ヒドロキシ一S−トリアゾロ〔1・5−a〕ピリミ
ジンを添加した。このハロゲン化銀乳剤に第2表に示す
ように増減色素を添加した。上記乳剤を青色に染色され
てないポリエチレンテレフタレート支持体の下塗された
両面に、支持体の各面上に一平方メートル当り銀3.5
tに相当するハロゲン化銀を含むように塗布した。各乳
剤層の上に一平方メートル当り1rの塗布量でゼラチン
保護層を設けた。セーフライト安全性を試験する目的で
、5Wのタングステン電灯とフジJf).7セーフライ
トフイルタ一(富士写真フイルム会社製)とを組み合せ
たセーフライトから1.5mの距離においてこの試料を
1分間露光した。500 Tf9 of 5-methyl J per kg of emulsion as stabilizer
Me[hydroxy-1S-triazolo[1.5-a]pyrimidine was added. To this silver halide emulsion were added dyes as shown in Table 2. The above emulsion was applied to both primed sides of an undyed blue polyethylene terephthalate support at a rate of 3.5 silver per square meter on each side of the support.
It was coated to contain silver halide corresponding to t. A protective layer of gelatin was applied over each emulsion layer at a coating rate of 1 r/m2. For the purpose of testing safelight safety, a 5W tungsten electric lamp and a Fuji Jf. This sample was exposed for 1 minute at a distance of 1.5 m from a safelight combined with a 7 safelight filter (manufactured by Fuji Photo Film Co., Ltd.).
実施例1と同様に現像した後、試料上の濃度を富士写真
フィルム製P型濃度型で測定した。得られた濃度値をセ
ーフライトカブリとして第2表に示した。また露光しな
い試料を同様に現像処理して濃度を測定した。得られた
濃度値(支持体濃度を含まず)を残色として第2表に示
した。第2表から、本発明の色素の組合せを用いた感光
材料はセーフライト光に安全であるに対し、UST9O
4、026の色素の組合せによるとセーフライト光でカ
ブリが生ずることが明らかである。After developing in the same manner as in Example 1, the density on the sample was measured using a P-type density type manufactured by Fuji Photo Film. The obtained density values are shown in Table 2 as safelight fog. Further, a sample that was not exposed to light was developed in the same manner and the density was measured. The obtained density values (not including support density) are shown in Table 2 as residual colors. From Table 2, it can be seen that the photosensitive materials using the dye combination of the present invention are safe to safelight light, whereas the UST9O
It is clear that the combination of dyes No. 4,026 causes fogging under safelight light.
また本発明の色素組合せを用いた感光材料は、迅速写真
処理後の残色が極めて少ないこともわかる。また、増感
色素(1−4)を使つた比較テスト黒7及び(−4)を
使つた比較テスト黒8はいずれもセーフライトによるカ
ブリの増加が著しいが、本発明の色素の組合せは螢光増
感スクリーンの特性とよく合致して透れた増感特性をも
ち、且つセーフライト光に対しても安全であることが理
解されるであろう。本発明の好ましい実施態様を列挙す
る。It can also be seen that the photographic material using the dye combination of the present invention has extremely little residual color after rapid photographic processing. In addition, comparative test black 7 using sensitizing dye (1-4) and comparative test black 8 using sensitizing dye (-4) both showed a significant increase in fog due to safelight, but the dye combination of the present invention It will be appreciated that it has transparent sensitizing properties that closely match the properties of photosensitizing screens, and is also safe against safelight light. Preferred embodiments of the invention are listed below.
但し、本発明はこれのみに限定されない。(1)特許請
求の範囲1又は2において、一般式(1)におけるR1
とR2の両方がスルホラジカルをもつアルキル基である
場合。However, the present invention is not limited to this. (1) In claim 1 or 2, R1 in general formula (1)
and R2 are both alkyl groups having a sulfo radical.
(至)特許請求の範囲1又は2において、一般式()に
おけるR3がスルホラジカルをもつアルキル基である場
合。(To) In Claims 1 or 2, when R3 in the general formula () is an alkyl group having a sulfo radical.
(3)特許請求の範囲1又は2において、ハロゲン化銀
粒子の平均粒子サイズが1.0μ〜2.0μの沃臭化銀
粒子からなるハロゲン化銀乳剤である場合。(3) In the case of claim 1 or 2, the silver halide emulsion is composed of silver iodobromide grains having an average grain size of 1.0 μm to 2.0 μm.
(4)特許請求の範囲1または2において、一般式(1
)におけるR1とR2の両方がスルホラジカルをもつア
ルキル基でかつ一般式()におけるR3がスルホラジカ
ルをもつアルキル基である場合。(4) In claim 1 or 2, general formula (1
) in which both R1 and R2 are an alkyl group having a sulfo radical, and R3 in the general formula () is an alkyl group having a sulfo radical.
(5)特許請求の範囲1又は2において、一般式′
(1)におけるR1とR2の両方がスルホラジカルをも
つアルキル基でかつ、一般式()におけるR3がスルホ
ラジカルをもつアルキル基であり、しかも写真感光材料
のハロゲン化銀乳剤層が平均粒子サイズ約1.0μ〜約
2.0μの沃塩臭化銀又は沃臭化銀粒子からなる場合。(5) In claim 1 or 2, the general formula '
Both R1 and R2 in (1) are an alkyl group having a sulfo radical, and R3 in the general formula () is an alkyl group having a sulfo radical, and the silver halide emulsion layer of the photographic light-sensitive material has an average grain size of approximately When it consists of silver iodochlorobromide or silver iodobromide grains of 1.0 μ to about 2.0 μ.
(6)実施態様(5)においてハロゲン化銀乳剤層が沃
素塩3,0モル以下を含む沃臭化銀粒子から成る場合。(6) In embodiment (5), when the silver halide emulsion layer is composed of silver iodobromide grains containing 3.0 mol or less of iodide salt.
(7)特許請求の範囲1において、螢光増感スクリ0
−ンに用いられた螢光体がテルビウムで活性化された
ガドリニウムオキシサルフアイド、テルビウムで活性化
されたイツトリウムオキシサルフアイド、テルビウムで
活性化されたランタンオキシサルフアイドの単独または
2種以上の混5 合物からなる場合。(7) In Claim 1, the fluorescent sensitizing screen 0
- The phosphor used in the phosphor is one or more of terbium-activated gadolinium oxysulfide, terbium-activated yttrium oxysulfide, and terbium-activated lanthanum oxysulfide. When it consists of a mixture.
第1図はX線写真フイルムを処理するのに通常用いられ
る安全光をうるための安全光フイルタ一の分光透過率曲
線を示す。FIG. 1 shows the spectral transmittance curve of a safe light filter commonly used for processing X-ray film.
Claims (1)
から成る写真感光材料を放射線螢光増感スクリーンと接
触させて放射線に露出した後写真処理することによつて
放射線写真像を得る方法において、螢光増感スクリーン
は最大発光波長が500〜570nmの範囲にあり且つ
発光エネルギーの少なくとも1/2が波長400nm以
上に分布するような螢光増感スクリーンであつて、上記
ハロゲン化写真乳剤層は下記一般式( I )で表わされ
る少くとも一つの増感色素と下記一般式(II)で表わさ
れる少くとも一つの増感色素を含有することを特徴とす
る放射線写真像を得る方法。 一般式( I )▲数式、化学式、表等があります▼ (式中、R_0はアルキル基を表わす。 R_1およびR_2はおのおのアルキル基を表わし、R
_1とR_2のうち少くとも1つはスルホラジカルをも
つアルキル基である。mは、1を表わす。一般式(II) ▲数式、化学式、表等があります▼ (式中、Zはベンズオキサゾール核を完成するに必要な
原子群;R_3はアルキル基を表わす。 Qは2−チオイミダゾリジン−2・4−ジオン核を完成
するに必要な原子群を表わす。)。[Scope of Claims] 1. A photographic material comprising a support and at least one silver halide photographic emulsion layer is exposed to radiation by contacting it with a radiation intensifying screen and then subjected to photographic processing. In the method for obtaining a photographic image, the fluorescent intensifying screen has a maximum emission wavelength in the range of 500 to 570 nm and at least 1/2 of the emission energy is distributed over a wavelength of 400 nm or more, The above-mentioned halogenated photographic emulsion layer contains at least one sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the following general formula (II). How to get the statue. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_0 represents an alkyl group. R_1 and R_2 each represent an alkyl group, and R
At least one of _1 and R_2 is an alkyl group having a sulfo radical. m represents 1. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, Z is the atomic group necessary to complete the benzoxazole nucleus; R_3 represents an alkyl group. Q is 2-thioimidazolidine-2. (Represents the atomic group necessary to complete the 4-dione nucleus.)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50040577A JPS599892B2 (en) | 1975-04-03 | 1975-04-03 | How to obtain a radiograph |
DE19762614352 DE2614352A1 (en) | 1975-04-03 | 1976-04-02 | RADIOGRAPHIC PROCEDURE AND SENSITIVE MATERIAL FOR THIS |
BE165815A BE840345A (en) | 1975-04-03 | 1976-04-02 | RADIOGRAPHIC PROCESS AND SENSITIVE MATERIAL USED FOR THIS PROCESS |
US05/672,947 US4040833A (en) | 1975-04-03 | 1976-04-02 | Radiographic process and sensitive material for the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50040577A JPS599892B2 (en) | 1975-04-03 | 1975-04-03 | How to obtain a radiograph |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS51115820A JPS51115820A (en) | 1976-10-12 |
JPS599892B2 true JPS599892B2 (en) | 1984-03-06 |
Family
ID=12584329
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP50040577A Expired JPS599892B2 (en) | 1975-04-03 | 1975-04-03 | How to obtain a radiograph |
Country Status (4)
Country | Link |
---|---|
US (1) | US4040833A (en) |
JP (1) | JPS599892B2 (en) |
BE (1) | BE840345A (en) |
DE (1) | DE2614352A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10856371B2 (en) | 2018-06-26 | 2020-12-01 | Midea Group Co., Ltd. | Wireless sensor in a microwave oven |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1591610A (en) * | 1976-10-07 | 1981-06-24 | Agfa Gevaert | Rapidly processable radiographic material |
JPS53106124A (en) * | 1977-02-28 | 1978-09-14 | Fuji Photo Film Co Ltd | Image recording by radiant ray |
US4425425A (en) | 1981-11-12 | 1984-01-10 | Eastman Kodak Company | Radiographic elements exhibiting reduced crossover |
JPS5938739A (en) * | 1982-08-27 | 1984-03-02 | Fuji Photo Film Co Ltd | Photographic silver halide emulsion used for direct positive |
JPS6041035A (en) * | 1983-08-16 | 1985-03-04 | Konishiroku Photo Ind Co Ltd | Photosensitive silver halide material for x-rays |
JPS6136744A (en) * | 1984-07-30 | 1986-02-21 | Fuji Photo Film Co Ltd | Treatment of silver halide photosensitive material for x-ray |
FR2574583B1 (en) * | 1984-12-07 | 1989-04-28 | Commissariat Energie Atomique | THICK LAYER RADIOLUMINESCENT SCREEN, MANUFACTURING METHOD THEREOF, AND DEVICE FOR CARRYING OUT SAID METHOD |
US4725529A (en) | 1985-04-30 | 1988-02-16 | Konishiroku Photo Industry Co., Ltd. | Developing inhibitor arrangment in light-sensitive silver halide color photographic materials |
AU590563B2 (en) | 1985-05-16 | 1989-11-09 | Konishiroku Photo Industry Co., Ltd. | Method for color-developing a silver halide color photographic light-sensitive material |
US5389502A (en) * | 1994-02-08 | 1995-02-14 | Eastman Kodak Company | Hardening developer for silver halide photography and development method |
FR2779242B1 (en) * | 1998-05-27 | 2000-06-30 | Eastman Kodak Co | NEW PRODUCT FOR INDUSTRIAL RADIOGRAPHY |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5638936B2 (en) * | 1973-07-16 | 1981-09-09 | ||
JPS5638938B2 (en) * | 1973-08-06 | 1981-09-09 | ||
US3912933A (en) * | 1973-10-17 | 1975-10-14 | Du Pont | Fine detail radiographic elements and exposure method |
-
1975
- 1975-04-03 JP JP50040577A patent/JPS599892B2/en not_active Expired
-
1976
- 1976-04-02 BE BE165815A patent/BE840345A/en not_active IP Right Cessation
- 1976-04-02 US US05/672,947 patent/US4040833A/en not_active Expired - Lifetime
- 1976-04-02 DE DE19762614352 patent/DE2614352A1/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10856371B2 (en) | 2018-06-26 | 2020-12-01 | Midea Group Co., Ltd. | Wireless sensor in a microwave oven |
Also Published As
Publication number | Publication date |
---|---|
BE840345A (en) | 1976-08-02 |
JPS51115820A (en) | 1976-10-12 |
US4040833A (en) | 1977-08-09 |
DE2614352A1 (en) | 1976-10-14 |
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